Anthraquinone dyestuffs and process for their manufacture



l5 or-unsubstituted benzene or naphthalene nucleus,

Patented July 23, 1935 ANTHRAQU NQ E .D SIU FS- ND P3 0 ESS FOR. THEIR snUFsoTUan AlbinPeter, Basel,switzerlanaj-ass gnor to the j. ,4 a firm of:Chemical Worksformerly Sandoz;Basel, 4i w Switzerland No Drawing. Applioatiorrjli ll'ay,$1934; serial iqm' 723,800. In Switzerland August 17,1933

27 claims; (01.2.60 64); l

Thepresent invention relates to new anthraquinone dyestuffs which'possess very valuable properties and to a-process for the manufacture of said dyestuffs. I

M It has been found that new anthraquinone dyestuffs can be prepared by treating with aldehydes of the aliphatic and aromatic series 'sucharyl aminoanthraquinones that contain a free 4'-position in the aryl nucleus; Such arylaminoanthraquinones possess, therefore, the following general formula I. I .or' i. V ..I

' A-NHR" wherein A represents a substituted or unsubsti tuted anthraquinone nucleusand R. a substituted that contains a free para-positionto the -NH'- group. The arylaminoanthraquinones which can beused-in-the present process may contain in the l-carbon to'a Q-carbon of the anthraquinone nu-' cleus, asthis occurs in the case of anthrapyridones, anthrap'yrimidones and' anthrapyri'r'nidines. V

"Such compounds are for instance l-phenylaminoanthraquinone, 1 aminol-phenylamino an'thraquino'ne,v 1 aminoe2 s'ulpho--phenylani ino-anthraquinone, l-'amino'-2-methy'l'- or" (Z-cyano) 1-4 -phenylaminoanthraquinone, 1 amino-2- bromol-phenylaminoanthraquinone, 1 -amino-2- bromo-B-ohloro-4-phenylaminoanthraquinone, 1- amino 4-a-naphthylaminoanthraquinone-2-sulphonic acid, carbethoxy-Z-sulpho 4 phenylamino-1-9 -anthrapyridone and also such compounds that are substituted inthe aryl nucleus, such as l-amino 2 sul'pho-4-(3f chlor ophenyl)' -aminoianthraquinone, l-amino 2 sulpho-e-(2methoxyphenyl) or -(-3'methy1phenyl) anthraquin one.

As aldehydes compounds such as formaldehyde, acetaldehyde, benzaldehyde, aminobenzaldehyde, nitroor chlorobenzaldehyde and .benzaldehyde sulphonic acids can be used. J Q

By treating the abovesaid anthraquinone com.- pounds with aldehydes newcondensation products are formed. The reaction which, takes place in this treatment may be represented by the fol,-

lowing scheme wherein A represents the anthraquinone'nucleus and Ra hydrogen, an aliphatic ora rar'oniatic group. H I

I The rivatives of di-f'jon triphenylmethane according to the aldehyde used for the condensation. The preparationof the" new compounds can be carried out by treating'the above saidarylaminoanthra quinones with aldehydes or with compounds yield ing'aldehyde'sin'a suitable solvent and in aneutralf'or aicid" medium; This, treatment can be carried'outunder heating the "solution or dispersion of the anthraquinonebodyup to 120 0., whereby temperatures between 30 and 100 C. will be preferably used.

,As solvents that can be used in the present process, water,; sulphuric and hydrochloric acid of various-concentrations acetic acid, and others rgmixtures thereof can be cited.

. The quantity; of a'ldehydes necessary for the condensation consistsof'one molecule thereof on twomoleculesof theanthraguinonebody, but it is .preferablefitoguse a small excess of aldehyde, in order to complete the reactionin a shorter time.

"The products obtained according to the present processjare, according -ty. i the starting products, soluble or insoluble in water. If it is intended to prepare water-soluble. dyestuffs, water-soluble starting-products are used, or sulphonic acid products obtained are, therefore,

groups are-introduced into the condensation prodv for the manufacture of anthraquinone dyestuffs consisting-Lain treating arylaminoanthraquinones having in the aryl group a free if-position, with aldehydes.

Another object of the present invention is the 'er c'essrertreating the said anthra'quinone bodies with aldehydesf iwhich process consists in that the 'anthraquinone' bodies are treated in form of solutions-orof' suspensions-with'aldehydes in a 'neutral 'or" acid" medium and preferably at a temperaturejof'3O tolOO 'GL I 1 Further-"the present invention comprises the new-condensation products obtained as above described, which are die or triphenylmethane derivatives and constitute, when soluble in water, WY a eetle;ere s s iq sein -1 .efibr e- The following examples,.without being limitative, illustrate the presentpro'cess, the. parts being by weight:

Example 1 20 parts of 1-amino-2-sulpho-Q phenylaminoanthraquinone are suspended in 100 parts of sulphuric acid of 70% and 10, parts of benzaldehyde are added thereto. The mixture is then treated on a water bath until a test shows that the precipitate formed is insoluble in boilingwater. The reaction mixture is then filtered, theprecipitaite washed with sulphuric acid of'70%. The condensation product is, thereupon, suspended in 500 parts, of water, neutralized with sodium hydioxide, filtered and'dried ,The sodium" salt of the dyestuff obtained in this manner is soluble in water and dyesw'oolfrom an acid bath in greenish-blue tints of excellent fastnes'sto milling and to light. 1 v I L I By replacing in this example'the benzalde'h'yde by 3- or 4-aminobenzaldeliyde or by 4-dimethyl hminobenzaldehyde, dyestufis are obtained which possess a better levelling power.

Example 2 20 parts of 1-amino-2-methyl-4-phenylaminoanthraquinone are suspended in- 200 parts of sulphuric acid of 80% and stirred at 60 C; with 11 parts of the sodium salt of benzaldehyde disulphonic acid. After a short time the condensation has taken place and the reactionproduct becomes soluble in water. The reaction mixture is then poured into water, filtered, the precipitate is suspended in water, neutralized and salted out. The dyestuff obtained dyes wool ingrey-blue tints of excellent fastness to millingandto light.

Example 3 Example 4 v parts, of 1-amino-2-sulpho- 4-iii' chlorophenyl) aminoanthraquinone are stirred on a boilingwatenbath with 200 parts of water, 2

parts of formaldehyde (40%) and parts of acetic acid, until a testshows thatthe aqueous solution does no morqbecome greener. "I'he'dyestufi thus produced is then isolated in usual manner. It dyes wool in ,blue tints of good fastness to light and to milling.

In the same manner condensation products from l-amino-Z-sulpho-4-(2--methoxy) or -(3- methyl) -phenylaminoanthraquinone may be obtained. The acetic acid used in this example can further be replaced by sulphuric, hydrochloric or formic acid.

, i t'l j A suspension of parts of carbethoxy-'2 sul pho-4-phenylamino-1:Q-anthrapyridone in 180 parts of sulphuric acid of 60% is heated at 60 C. under stirring with 0.5 parts of paraiormaldehyde, until a test shows that the product is no more soluble in cold water. The precipitate is then filtered, neutralized and isolated in the usual manner by salting it out from its aqueous solution. It dyes wool in clear violet tints of good fastness to milling and to light.

Example 6 parts 'of 1-aminol-phenylaminoanthraquinone are suspended in 180 parts of sulphuric acid of 10% and heated up to 60 C. with 1 part of paraformaldehyde. 'The condensation product thus obtained gives a greener shade in ethyl acetate than the starting product. It is isolated by filtration and sulphonated with weak oleum at 40 C. The dyestufi thus produced dyes wool" in reddish-blue tints of excellent fastness to light and to milling.

Example 10 parts of 1-amino-4-phenylaminoanthraquinone-2-sulphonic acid, 200 parts of water and 2 parts of formaldehyde of 40% are heated for 24 hours under stirring on a water bath. After this time the dyestufi is formed andis isolated by salting out. It is identical with the dyestufi prepared according to Example 2. r

The condensation of the sodium salt of the l-aminoi- (3' -methylphenyl) aminoanthraquinone-Z-sulphonic acid with formaldehyde can be carried out in the same manner.

Example 8 20 parts of l-phenylaminoanthraquinone are dissolved in 150 parts of sulphuric acid of 80% and stirred at 60 C. during 1 hours with 1.2 parts of paraformaldehyde. The reaction mixtureis poured into 500 parts of water and the condensation product isolated by filtration.

By sulphonating it with oleum at 45 C.,a dyestufi is obtained which dyes wool and silk in brown-red tints.

What I claim is:-

1. A process for the manufacture of anthraquinone compounds, consisting in treating with an aldehyde selected from the class consisting of aliphatic and aromatic aldehydes andin presence ofa diluting agent arylaminoanthraquinones of the general formula wherein A represents an anthraquinone nucleus and R an aromatic nucleus of the benzene and naphthalene series possessing a free para-position to the group -NH.

-2. A process for the manufacture of anthraquinone compounds, consisting in treating with an aldehyde selected from the class consisting of aliphatic and aromatic aldehydes and. in presence of a diluting agent of acid nature arylaminoanthraquinones of the general formula.

wherein A represents an anthraquinone nucleus and R an aromatic nucleus of the benzene and naphthalene series possessing a free para-position to the group NH-. 3. A process for the manufacture of anthraquinone compounds, consisting in treating-with amino, vhalogen and sulpho groups.

the general formula egooa vee an aldehyde"and in' 'presnce of sulphuric acid arylaminoanthraquinones of the general formula wherein A represents an anthraquinone nucleus andgR'anaromatic nucleus of the benzene and naphthalene, series possessing a free para-position tofthegrou'p NH---.' 1

4. A-uprocess for the manufacture of anthraquinone compounds,"consisting -in treating with an aldehyde and in presence of sulphuric acid of 40 to 100% strength arylaminoanthraquinones of wherein A represents an anthraqu'mone nucleus" and R an aromatic nucleus of the benzene'and naphthalene series possessing a free para-position to the group tNH-.l Y

' 5. A processfor the manufacture ofanthraqui none compounds, consisting inj treatiung with an aldehyde at a temperaturejof 3 0 tov 100 Q' andtin presence of, sulphuric acid of 40 to 100% strength arylarninoanthraquirionesiof the general formula wherein A represents an anthraquinone'nucleus and R an aromatic nucleus of the benzene and naphthalene series possessing a free paraposition'to-the'group -:NH'; v H H 6. Aprocess for themanufacture of anthraquinone compounds consisting in treating with an aldehyde at a temperature of 30 to 100 C. and in presence of sulphurieacid of ,40 to 100% strength jarylaminoanthraquinones' er the'igeri'eral formula I v .L

wherein A represents an anthr'aquinone nucleus and X represents hydrogen, alkyl, alkoxy, acyl 7. A process for the 'rnanufactureiof anthraquinon'e compounds, consisting in treating with an aldehyde at a't'mperature of 30 to 100 C. and

in presence of sulphuric acid of 40 to 100% strength arylaminoanthraquinones of the general formula wherein Y represents hydrogen-Q alkyl; alk,ory,

halogen, cyano and sulpho, Z represents hydrogen, halogen, hydr,oxy,. alkoxy, amino, acyl-amino and sulpho, and X represents hydrogen, alkyl,

alkoxy, acyl aminorhalogen and sulpho groups.

8. Afprocess for the manufacture of anthraquinone -;.compounds,-consistingim treating with an aldehyde; atja .temperaturepfzsBW. tel 100%,.(1.

and in presence-of sulphuric acid of 40: to. 10.0%

eral formula -i 40 10o% strength.

strength arylaminoanthraquinones of, the 1 gen- QWherein Y represents hydrogen, ,alkyl,; alko y halogemcyano and sulpho and'X represents hydrogen, alkyl, alkoxy, acyl amino, halogen and sulpho groups;

9. Aprocess' for the manufacture of anthraquinonecompounds, consisting" in treating with an aldehydeat a temperature of 30 to 100 C. and in presence'of sulphuric acid of 40 to 100% strength an arylaminoanthraquinone of the I: .7 1 I t {in V 10. #:IJI'QCQBSS for the'v 'mariuiacture of ,anfa'n thra'quinone' ayeaufr; consisting in" treating Q1- amino-4-phenylaminoanthraquinone 2 sulphonic acid with formaldehyde at a temperature .of 30 to 100? C. and in presence-0f sulphuric acid of 40 l00% strength. I v 11 A process for the manufacture of an. anthraquinone ldyestuff, consisting in treating 1-. amino-'4-pheny1aminoanthraquinone 2-sulphonic acid with acetaldehyde at-a temperature of 30 to 100 C. andlin presence of sulphuric acid of 12. A process for the manufacture of an anthraqu n n d est ns sti -in r ngam a- ,with 3-aminobenzaldehyde atfa {temperature of 30 l00 0.; and in presence oflsulphuric acid of Q 1 .6 l hi. 1 13.;flhesa thraqu nonec mpo nds ith 's eraliormulal.

wherein A represents an anthraquinonenucleus, R represents an aryl nucleus of the'benzene and naphthalene series and B represents hydrogen,

alkyl and aryl, said compounds constituting in dry state yellow orange, red, violet to dark powders; which,-'when they contain sulphonic acid shades.

14. The anthraquinone compounds of the general fiormula I I wherein A represents an anthraduinone nucleus,

, groups, are soluble'in water and dye animal fibres in yellow-orange, red-yiolet blue to green-blue l] to 13 represents hydrogen, .alkyl and aryl, and X represents hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups, said compounds constituting in dry state yellow-orange, red violet to dark powders, which, when they contain sulphonic acid groups, are soluble in water and dye animal fibres in yellow-orange, red-violet, blue to green-blue shades.

15. The anthraquinone compounds of the general formula wherein B represents hydrogen, alkyl and aryl, X represents hydrogen, alkyl, alkoxy,'acylamino, halogen and sulpho groups and Y represents hydrogen, alkyl, alkoxy, halogen, cyano and sulpho groups, said compounds constituting in dry statedarkpowders which, when they contain sulphonic acid groups are soluble in water and dye animal fibres in violet to green blue shades of excellent fastness properties.

17. The anthraquinone compounds of the general formula wherein B represents hydrogen, alkyl and aryl and X represents hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups, said compounds constituting in dry state dark powders which are soluble in water with a blue coloration and dye animal fibres in reddish-blue to greenish-blue shades of excellent fastness properties. V 1

'18. The anthraquinone compound of the formula i HI IOCHrO-l ZIlwhich constitutes in dry state a dark powder, soluble in water with a greenish-blue and in concentrated sulphuric acid with a dull blue-green coloration and which dyes animal fibres in blue shades of excellent rastness' properties.

19. The anthraquinone compound of the formula c lTIHz C O fi H I n OtQ O CH: I which constitutes in dry state a dark powder soluble in water with a greenish-blue and in concentrated sulphuric acid with a greyish-green coloration and which dyes animal fibres in blue shades of excellent fastness properties.

20. The anthraquinone compound of the formula 0 NH: H t I a S0311 Hols wherein A represents an anthraquinone nucleus andX represents a shade modifying substituent selected from the group'consisting of hydrogen,

alkyl, alkoxy, acylamino, halogen and sulpho groups. a

22. A process for the manufacture of anthraquinone dye compounds, consisting in treating with an aldehyde ,at a temperature of 30 to C. and in presence of sulphuric acid of 40 to 100% strength arylaminoanthraquinones of the general formula wherein Y represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, halogen, cyano and sulpho, Z

represents a shade modifying substituent selected from the group consisting of hydrogen, halogen, hydroxy, alkoxy, amino, acylamino and sulpho, and X represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups. I

23. A process for the manufacture of anthraquinone dye compounds, consisting in treating with an aldehyde at a temperature of 30 to 100 C. and in presence of sulphuric acid of 40 to 100% strength arylaminoanthraquinones of the general formula (H I NH: U I

X X p I 1 l wherein Y represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, halogen, cyano and sulpho and X represents a shade modifying substituent selected from the groupconsisting of hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups.

24. The anthraquinone dye compounds of the general formula r r X X H i B l X X X wherein A represents an anthraquinone nucleus, B represents hydrogen, alkyl and aryl and X represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl,

alkoxy, acylamino, halogen and sulpho groups,

said compounds constituting in dry state yellow- X x x X o I l H l II J) X X X X orange,-red violet to dark powders, which,when they contain sulphonic acid groups, are soluble in water and dye animal fibres in yellow-orange, red-violet, blue to green-blue shades. I

25. The anthraquinone dye compounds of' th general formula wherein B represents hydrogen, alkyl and aryl, X represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, substituted amino, halogen and sulpho groups, Y represents a shade modifying substituent selected from the group consisting of i n e i X X X X l r o o X X I X wherein B represents hydrogen, alkyl and aryl, X represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups and Y represents a shade modifying substituent selected from the group consisting of hydrogen, alkyl, alkoxy, halogen, cyano and sulpho groups, said compounds constituting in'dry state dark powders which, when they contain sulphonic acid groups are soluble in water and dye animal fibres in violet to green-blue shades of excellent fastnessv properties.

27. The anthraquinone dye compounds of th general formula O NH:

v X X x 'X wherein B represents hydrogen, alkyl and aryl 0 I HO3$-- O X X I'T QNH 0 s and X represents a shade modifying substituent I selected from the group consisting of hydrogen, alkyl, alkoxy, acylamino, halogen and sulpho groups, said compounds constituting in dry state dark powders which are soluble in water with a 'blue coloration and dye animal fibres in'reddishblue to greenish-blue shades of excellent fastness properties.

'- ALBIN PETER. 

